CN105711017B - A kind of method for preparing polymeric micro-fluidic chip based on hydrogel 3D printing - Google Patents
A kind of method for preparing polymeric micro-fluidic chip based on hydrogel 3D printing Download PDFInfo
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- CN105711017B CN105711017B CN201610088589.4A CN201610088589A CN105711017B CN 105711017 B CN105711017 B CN 105711017B CN 201610088589 A CN201610088589 A CN 201610088589A CN 105711017 B CN105711017 B CN 105711017B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C39/00—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor
- B29C39/02—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor for making articles of definite length, i.e. discrete articles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C33/00—Moulds or cores; Details thereof or accessories therefor
- B29C33/38—Moulds or cores; Details thereof or accessories therefor characterised by the material or the manufacturing process
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C33/00—Moulds or cores; Details thereof or accessories therefor
- B29C33/38—Moulds or cores; Details thereof or accessories therefor characterised by the material or the manufacturing process
- B29C33/3835—Designing moulds, e.g. using CAD-CAM
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C33/00—Moulds or cores; Details thereof or accessories therefor
- B29C33/38—Moulds or cores; Details thereof or accessories therefor characterised by the material or the manufacturing process
- B29C33/3842—Manufacturing moulds, e.g. shaping the mould surface by machining
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y10/00—Processes of additive manufacturing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y50/00—Data acquisition or data processing for additive manufacturing
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/10—Esters
- C08F120/12—Esters of monohydric alcohols or phenols
- C08F120/14—Methyl esters, e.g. methyl (meth)acrylate
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Abstract
The invention belongs to micro fluidic chip technical field, specially a kind of method for preparing polymeric micro-fluidic chip based on hydrogel 3D printing.Prepare 3D printing carragheen or agar thermal reversion hydrogel, by adjusting hydrogel concentration and using crosslinking agent, with after improving its mechanical strength, reducing its thawing viscosity and accelerate its it is cooled after gelation rate.Using structural units such as the channel network of Software for Design micro-fluidic chip, solution hole, reactors, design document, which exports, gives high-accuracy water gel 3D printer, and hydrogel, which is printed upon on bottom plate, can obtain hydrogel male mold.Macromolecule prepolymer is mixed to obtain to mold solution with curing agent, is poured on formpiston, and cover cover board, keeps it molten full of mold with the gap of formpiston, curing and demolding obtains micro-fluidic chip substrate, and micro-fluidic chip finished product is obtained after being encapsulated with cover plate.The polymeric micro-fluidic chip of the materials such as polymethyl methacrylate, dimethyl silicone polymer, epoxy resin can be processed using this method.
Description
Technical field
The invention belongs to micro fluidic chip technical fields, and in particular to a kind of polyalcohol microflow control based on hydrogel 3D printing
Chip preparation method.
Background technology
Micro-fluidic chip mainly uses glass, quartz and polymer to make [1], and wherein glass and quartzy micro-fluidic chip is logical
Frequently with the method processing that photoetching is combined with chemical etching, technology and equipment requires high, it is difficult to produced in enormous quantities using mold,
Price is more expensive, limits its extensive use.Then, polymeric micro-fluidic chip is developed and payes attention in recent years, can
[2] are produced in batches by the technologies low cost such as injection molding, stamp and casting using mold.Polymer for processing micro-fluidic chip
There is polymethyl methacrylate（PMMA）, dimethyl silicone polymer（PDMS）, makrolon（PC）, polystyrene（PS）Deng [3],
Wherein polymethyl methacrylate and dimethyl silicone polymer are two kinds of more common materials.Polymeric micro-fluidic chip is due to can
Batch low cost processing has wide in biological medicine analysis, environmental monitoring, food and medicine analysis and clinical diagnosis etc.
Application prospect.
The processing generally use casting method of dimethyl silicone polymer micro flow control chip, i.e., by commodity performed polymer and crosslinking curing
It after agent mixing, is formed by die casting, technics comparing is ripe.The processing technology of thermoplastic polymer micro-fluidic chip has hot pressing
[4], [5], laser ablation [6] etc. are molded, wherein hot-pressing technique uses more at present, and silicon formpiston or metal positive are using micro electronmechanical
Processing technology makes.Hot pressing is higher to the requirement of mechanical strength of Chip mold, and silicon mould is frangible, and usual hot pressing number is no more than 50
Secondary [7] need to use micro electro mechanical processing technology and equipment, and cost of manufacture is high, and step is various, and every formpiston need to be processed individually.It is special
Not when casting method prepares polymeric micro-fluidic chip, silicon and metal and the polymeric micro-fluidic chip intermolecular forces of forming compared with
Greatly, demoulding is very difficult, often results in the damage of mold and chip.Then, using cheap materials processing can batch low cost life
The formpiston of production has important practical significance.
Macromolecule hydrogel is mainly with natural macromolecular material（Such as agar, carragheen, gelatin）With artificial synthesized high score
Sub- material（Such as polyvinyl alcohol）Have the characteristics that of low cost and be easily worked containing a large amount of moisture for carrier, after discarding
Can natural degradation in the environment, use it for the processing of micro-fluidic chip, chip manufacture cost can be greatly lowered.
3D printing is a kind of digitlization rapid shaping technique of high speed development in recent years.According to printing shaping principle, more
It is ripe and have an actual application prospect has 5 kinds, including Deformation In The Fdm Process（FDM）, stereolithography apparatus（SLA）, layering
Entity manufactures（LOM）, three-dimensional powder bonding（3DP）And selective laser sintering（SLS）.Currently, the mostly of commercial type are molten
Melt accumulation molding（FDM）3D printer, mainly with acrylonitrile-butadiene-styrene (ABS) plastics（ABS）And polylactic acid（PLA）As
Printed material.Then, we expect that FDM technology 3D printing is used to melt hydrogel to prepare cheap micro-fluidic chip hydrogel
Formpiston with facilitating chip processing flow, and uses casting method replica polymer micro-fluidic chip.But through consulting domestic and foreign literature,
It is not yet found that using the report of 3D printing hydrogel male mold processable polymer micro-fluidic chip.The present invention establishes one kind and is based on
The method for preparing polymeric micro-fluidic chip of hydrogel 3D printing, the photoetching and micro-processing technology without using costliness and equipment,
Have the advantages that simple for process and of low cost, has good answer in the batch low cost manufacture field of polymeric micro-fluidic chip
Use foreground.
Bibliography
[1]Ren KN, Zhou JH, Wu, HK. Accounts of Chemical Research, 2013, 46
(11): 2396-2406.
[2]Xu BB, Zhang YL, Xia H, Sun HB. Lab on A Chip, 2013, 13(9): 1677-
1690.
[3]Chen Y, Zhang LY, Chen G. Electrophoresis, 2008, 29(9): 1801-1814.
[4]Chen, QW, Zhang LY, Chen, G. RSC Advances, 2014, 4(99): 56440-
56444.
[5]Du LQ, Chang HL, Song MC, Liu C. Microsystem Technologies-Micro-
and Nanosystems-Information Storage and Processing Systems, 2012, 18(6): 815-
822.
[6]Hong TF, Ju WJ, Wu MC, Tai CH, Tsai CH, Fu LM. Microfluidics and
Nanofluidics, 2010, 9(6): 1125-1133.
[7] leaf the U.S. and Britain, Yin Xuefeng just start the processing of human relations silicon-mold of microfluid chips, micrometer-nanometer processing technology,
2004,(3): 59-64.。
Invention content
It is an object of the invention to propose a kind of polymeric micro-fluidic chip simple for process based on hydrogel 3D printing
Preparation method cannot be only used for the batch low cost processing of chip, it may also be used for the single polymer miniflow with labyrinth
The personalized designs and customization for controlling chip are processed.
Method for preparing polymeric micro-fluidic chip proposed by the present invention based on hydrogel 3D printing, the specific steps are：
（1）It prepares 3D printing agar thermal reversion hydrogel or carragheen thermal reversion hydrogel, the component of hydrogel is main
For water, crosslinking agent and carragheen or agar etc..It can make preparation by adjusting the concentration of hydrogel and using dosage of crosslinking agent
3D printing has certain mechanical strength with hydrogel, and solution viscosity is low after thawing and gelation rate is fast after cooling down, in order to molten
Melt accumulation 3D printing.
（2）Using computer aided design software（Such as AutoCAD）Channel network, the solution of design and micro-fluidic chip
The corresponding formpiston of the structural units such as hole, reactor generates the design document that 3D printer can be directly read, such as binary
Stl file.
（3）After 3D printing carragheen or the heating fusing of agar thermal reversion hydrogel, injection carries constant temperature heating device
In stainless steel syringe, syringe is mounted on fixed in the screens of 3D printer.It is walked by the charging of hydrogel 3D printer
Stepper motor pushes syringe piston to squeeze out the hydrogel of thawing by print head.The X-axis of 3D printer, three of Y-axis and Z axis
Stepper motor is advanced according to the G code generated by design document, and the hydrogel layering of thawing is printed upon glass or polymer bottom
On plate, hydrogel male mold corresponding with structural units such as micro-fluidic chip channel network, solution hole, reactors is obtained.
（4）Macromolecule prepolymer is mixed to obtain to mold solution with curing agent, mold solution can be the first containing photoinitiator
Base methyl acrylate pre-gathering solutions, the dimethyl silicone polymer oligomer containing curing agent or the epoxy resin prepolymer containing curing agent
Etc. can mold transparent polymer pre-polymer solution.Mold solution is poured on 3D printing hydrogel male mold, cover cover board make its with
Gap between hydrogel male mold is full of mold solution, waits for mold solution curing and demolding, obtains the miniflow with microchannel structure
Control chip substrate；By gained substrate and the encapsulation of the micro-fluidic chip cover plate of same material to get polymeric micro-fluidic chip finished product.
In the present invention, step（1）Described in hydrogel high molecular material select carragheen or agar etc., prepare water
There is gel thermal reversibility, heating and melting to be cooled to gel point and be rapidly solidificated into gel, molten in order to the 3D of hydrogel male mold
Melt printing and is cooled and shaped on bottom plate.The present invention selects carragheen and agar both natural macromolecular materials preparation water-setting
Glue has the characteristics that be easy fast gelation when the small easy printing of viscosity and temperature are less than gel point after melting.OK a karaoke club hydrogel
Potassium chloride and borax are selected respectively with the crosslinking agent of agar hydrogel.The formula of OK a karaoke club hydrogel：Carragheen 0.5-3%, crosslinking
Agent potassium chloride 0.1-2%, water surplus；The formula of agar hydrogel：Agar 0.5-5%, crosslinking agent borax 0.1-1%, water surplus.It presses
Hydrogel high mechanical strength prepared by both formulas, can be used for the cast molding of polymeric micro-fluidic chip.
In the present invention, step（2）Described in design software can be selected can export the three of binary system STL format design files
Tie up design software, such as AutoCAD, 3DMAX, PROE, UG, SOLIDWORKS.For design with micro-fluidic chip channel network,
The three-dimensional structure of the corresponding formpiston of the structural units such as solution hole, reactor.
In the present invention, step（3）Described in 3D hydrogel printers be commodity high-accuracy water gel printer, print head
Internal diameter be 50-150 microns, hydrogel male mold can be directly printed on bottom plate according to STL design documents.And only there is miniflow
The position of the structural units such as channel prints hydrogel, can substantially save time-write interval and printed material.It is beaten using 3D printer
It is respectively 70-90 DEG C and 60- to the heating temperature of OK a karaoke club hydrogel and agar hydrogel in syringe when printing hydrogel male mold
80℃.Syringe constant temperature heating device includes electrical heating elements, thermocouple and temperature controller.
In the present invention, step（4）Described in using 3D printing hydrogel male mold as the polymeric micro-fluidic chip base of template
When piece cast molding, macromolecule pre-gathering solutions are clipped in 3D printing hydrogel male mold and cover board with the mold solution that curing agent is made into
Between, the gap of hydrogel male mold and cover board is 0.25-1.0 millimeters and is full of mold solution, waits for mold solution curing and demolding, i.e.,
Obtaining has the isostructural micro-fluidic chip substrate of microchannel.
In the present invention, step（4）Described in polymeric micro-fluidic chip encapsulation when, the identical of solution connection holes will be drilled with
The polymer cover plate of material has channel isostructural with the micro-fluidic chip substrate prepared by 3D printing hydrogel male mold mold
It closes after being aligned on one side, is encapsulated using technologies such as hot pressing, bonding or bondings, then deburring obtains polymeric micro-fluidic chip.
Method for preparing polymeric micro-fluidic chip proposed by the present invention based on hydrogel 3D printing, be described in further detail as
Under:
First, 3D printing carragheen thermal reversion hydrogel or agar thermal reversion hydrogel, primary aqueous, crosslinking need to be prepared
Agent and carragheen or agar etc..The 3D printing of preparation can be made to use by adjusting the concentration of hydrogel and using dosage of crosslinking agent
Hydrogel has certain mechanical strength, so that the hydrogel male mold that printing obtains is had certain intensity, it is micro- to can be used for polymer
The cast molding of fluidic chip.Solution viscosity is low after also requiring hydrogel to melt, and melts printing convenient for 3D printer.In addition, also
Needing the hydrogel melted to print on cold bottom plate 9, gelation rate is fast after cooling, in order to accumulation molding.Pass through many experiments
Screening, the present invention select carragheen and agar both natural macromolecular materials preparation hydrogel, have viscosity little Rong after melting
Gelation rate fast feature when easily printing and temperature are less than gel point.The crosslinking agent of OK a karaoke club hydrogel and agar hydrogel is distinguished
Select potassium chloride and borax.The formula of OK a karaoke club hydrogel：Carragheen 0.5-3%, crosslinking agent potassium chloride 0.1-2%, water surplus；Fine jade
The formula of fat hydrogel：Agar 0.5-5%, crosslinking agent borax 0.1-1%, water surplus.The 3D printing water prepared by both formulas
Gel have the characteristics that high mechanical strength and melt rear viscosity it is low and be gelled it is fast, be suitable for fused deposition 3D printing and polymer it is micro-
The cast molding of fluidic chip.
Using the design of computer aided design software AutoCAD2016 three-dimensional modelings and micro-fluidic chip channel network, molten
The corresponding hydrogel male mold of the structural units such as fluid apertures, reactor, the design such as attached drawing of typical list right-angled intersection micro-fluidic chip
1, by split tunnel 2, sample intake passage 7 and solution connection holes（1 and 4-6）It constitutes, microchannel width is 50-500 microns, solution
Connect 1-3 millimeters of bore dia.The height of formpiston is 30-300 microns.The design document output of acquisition is that high-accuracy water gel 3D is beaten
The binary system STL formatted files that print machine can be directly read are stored in SD card, are inserted into hydrogel 3D printer card reader and open
Dynamic printing.
As shown in Fig. 2, it before printing, is dried after first cleaning glass or polymer base 9, is placed in 3D printer bottom
It is fixed on print platform and adjusts level.3D printing carragheen thermal reversion hydrogel or agar thermal reversion hydrogel are heated to
After 80-95 DEG C of fusing, in stainless steel syringe of the injection with constant temperature heating device, syringe is mounted on hydrogel 3D printing
It is fixed in the screens of machine, push syringe piston that the hydrogel of thawing is passed through printing by the charging stepper motor of 3D printer
Head squeezes out.Three X-axis of 3D printer, Y-axis and Z axis stepper motors are according to by design document（Such as stl file）The G code of generation
It advances, the hydrogel of thawing is printed upon on bottom plate 9, is obtained and the structures lists such as micro-fluidic chip channel network, solution hole, reactor
First corresponding hydrogel male mold 8.
3D hydrogel printers used in the present invention are commodity high-accuracy water gel printer, and the internal diameter of print head is 50-
150 microns, hydrogel male mold 8 can be printed directly on bottom plate 9 according to STL design documents（See attached drawing 2）.Due to only having miniflow
The position of the structural units such as channel prints hydrogel, can substantially save time-write interval and printed material.It is more importantly anhydrous
The part of gel is rigid and smooth glass plate or plastic plate, can be obtained by casting method smooth with knots such as microchannels
The substrate of structure is conducive to subsequent encapsulation.When the 3D printer printing hydrogel male mold that the present invention uses, to OK a karaoke club in syringe
The heating temperature of hydrogel and agar hydrogel is controlled as 70-90 DEG C and 60-80 DEG C, the heated at constant temperature dress on syringe
It sets including electrical heating elements, thermocouple and temperature controller etc..
Macromolecule pre-gathering solutions are mixed to obtain to mold solution 10 with curing agent, due to the use of be hydrogel male mold, select
Mold solution need to cure below hydrogel melt temperature, and require curing reaction heat release seldom.Meet the normal of these conditions
There are the methyl methacrylate pre-polymer solution containing photoinitiator, the dimethyl silicone polymer containing curing agent oligomeric with mold solution
Object or epoxy resin etc. containing curing agent, it is curable below hydrogel melt temperature in less than the present invention.Light will be dissolved with
Initiator benzoin ethyl ether（The 0.1-0.3% of methyl methacrylate quality）And azodiisobutyronitrile（Methyl methacrylate matter
The 0.1-0.3% of amount）Methyl methacrylate solution heated 20-60 minutes in 70-90 DEG C of water-bath, obtain containing light-initiated
The methyl methacrylate pre-polymer solution of agent；And the dimethyl silicone polymer oligomer mold solution containing curing agent is by commodity
Dimethyl silicone polymer oligomer（Such as 107 room temperature vulcanization dimethyl silicone polymers）With curing agent tetraethoxysilance and accelerating agent two
Dibutyl tin laurate mixing obtains, and the content of wherein tetraethoxysilance and dibutyl tin laurate is respectively 5% and 1-2%；
Epoxy resin pattern solution containing curing agent uses commodity bisphenol A epoxide resin（Such as E51 epoxy resin）With curing agent ethylene diamine
It is mixed with, wherein the content of ethylenediamine is 8-12%.
Mold solution 10 is selected according to the requirement of pre-prepared micro-fluidic chip, is poured on 3D printing hydrogel male mold 8, and cover
Upper cover plate 11.Cover board 11 and the gap of hydrogel male mold 8 are controlled by gasket in 0.25-1.0 millimeters of ranges, and are required between being somebody's turn to do
Gap is full of mold solution 10, when 10 solidified forming of mold solution and demoulds back shroud 11 as polymeric micro-fluidic chip substrate 13
A part.Then, solution is beaten in the end corresponding to 13 channel of microchannel substrate on the polymer cover plate 15 of same material
Connecting hole 1,4,5 and 6（See attached drawing 1, aperture 1-3 millimeters）.For cast between hydrogel male mold 8 and cover board 11 containing light-initiated
The methyl methacrylate pre-polymer solution of agent irradiates 30 under 365 nanometers of ultraviolet light at room temperature using glass film plates 9
Minute fully hardened can obtain polymethyl methacrylate micro flow control chip substrate 13, by the polymethyl with solution connection holes
Sour methyl esters cover plate 15 is aligned with substrate 13 to be closed, structured one side in centre, using after infrared ray packaging by hot pressing it is micro-fluidic
Chip finished product 14 is shown in attached drawing 5.And for dimethyl silicone polymer oligomer and epoxy resin, once curing agent is added, solidification
Reaction starts immediately, it is necessary to prepolymer and curing agent be mixed simultaneously vacuum outgas before chip of casting.Casting polydimethylsiloxanes
When alkane micro-fluidic chip substrate 13, the dimethyl silicone polymer between hydrogel male mold 8 and cover board 11 is cast in infrared radiation
Mold solution, temperature are controlled at 40-50 DEG C, and mold solution can be cured as elastomer in 10-30 minutes.Bottom plate 9 need to be to apply
There is remover（Such as the sodium stearate solution of 0.1-1%）Polymethyl methacrylate plate, demould to obtain dimethyl silicone polymer miniflow
Control chip substrate 13.Substrate 13 has the one side and one in channel after wavelength is to be irradiated 10-40 minutes under 365 nanometers of ultraviolet light
Piece is equipped with solution connection holes 1,4,5 and 6 with size through UV treatment（See attached drawing 1, aperture 1-3 millimeters）Poly dimethyl
Siloxanes cover plate is aligned, and pressurization encapsulation at room temperature can obtain dimethyl silicone polymer micro flow control chip finished product 15.For casting in
Epoxy resin pattern solution between hydrogel male mold 8 and transparent epoxy resin cover board 11, with infrared radiation, and temperature control exists
40-50 DEG C, it can polymerize completely in 10-30 minutes, bottom plate 9 can be glass plate or polymethyl methacrylate plate, demould to obtain ring
Oxygen resin micro-fluidic chip substrate, substrate 13 obtained can be with a piece of same size epoxy resin cover plates 15 for being coated with absolute ethyl alcohol
Micro-fluidic chip 14 is obtained by packaging by hot pressing in 100-150 DEG C of temperature range.
Present invention firstly provides and be successfully established the method for preparing polymeric micro-fluidic chip based on hydrogel 3D printing,
Elastic thermal reversion hydrogel male mold is prepared for using hydrogel 3D printing technique, and is used successfully to pouring for polymeric micro-fluidic chip
Casting processing.This digitlization rapid shaping technique of 3D printing is used for the preparation of hydrogel male mold by the present invention, without expensive light
Quarter and micro electro mechanical processing technology and equipment, can bulk print.Since hydrogel mold materials are of low cost, forming is easy and can give birth to
The advantages of object is degraded not only has good application prospect in the processing of the batch low cost of polymeric micro-fluidic chip, also can be used
It is processed in the customization of the individual polymer micro-fluidic chip with special construction.The present invention only print micro-fluidic chip have it is logical
Road and functional unit（Such as reactor）Part, compared with micro-fluidic chip integrally prints, can substantially shorten the time-write interval, reduce
Energy consumption and the consumption for reducing printed material.
Description of the drawings
Fig. 1 is the single right-angled intersection micro-fluidic chip plane design drawing of typical case that the present invention processes.
Fig. 2 is to prepare polyalcohol microflow control based on 3D printing hydrogel male mold 8 and 10 in situ Polymerization method of mold solution
The flow chart of chip.Wherein,（A）3D printing carragheen hydrogel male mold or agar water on glass film plates or polymer base 9
Gel formpiston 8；（B）Mold solution 10 is cast on hydrogel male mold 8；（C）Cover board 11 is covered in mold solution 10, makes mold
Solution 10 is full of the gap between the two；（D）With wavelength be 365 nano-ultraviolet lights or infrared ray 12 cause in situ Polymerization obtain it is micro-
Fluidic chip substrate 13；（E）Separating micro-fluidic chip substrate 13 removes the hydrogel in channel；（F）By micro-fluidic chip substrate
13 with the polymer cover plate 15 of same material by encapsulating to obtain polymeric micro-fluidic chip finished product 14.
Fig. 3 is to be led to using polymethyl methacrylate micro flow control chip substrate prepared by 3D printing carragheen hydrogel male mold
The section microscope photo in road.
Fig. 4 is to encapsulate to lead to using polymethyl methacrylate micro flow control chip prepared by 3D printing carragheen hydrogel male mold
The section microscope photo in road.
Fig. 5 is the polymethyl methacrylate micro flow control chip material object photo prepared using 3D printing carragheen formpiston.
Fig. 6 is the electrophoresis pattern containing 18 mixed standard solution of 0.5 mM estriol 16, oestrone 17 and estradiol.
Figure label：1 is sample solution hole, and 2 be separation microchannel, and 3 be to be connected with 7 and solution containing microchannel 2
Hole Isosorbide-5-Nitrae, 5 and 6 micro-fluidic chip, 4,5 and 6 be buffer solution hole, and 7 be sample introduction microchannel, and 8 be hydrogel male mold, and 9 are
Glass film plates or polymer base, 10 be the mold solution being made of macromolecule prepolymer solution and curing agent, and 11 be cover board, 12
It is polymeric micro-fluidic chip substrate for ultraviolet light or infrared ray, 13,14 be polymeric micro-fluidic chip, 15 polyalcohol microflow controls
Chip cover plate, 16 be estriol, and 17 be oestrone, and 18 be estradiol.
Specific implementation mode
The present invention is further described below by embodiment and attached drawing：
Embodiment 1,3D printing carragheen hydrogel male mold answering in polymethyl methacrylate micro flow control chip preparation
With
First, 3D printing carragheen thermal reversion hydrogel, primary aqueous, crosslinking agent potassium chloride and OK a karaoke club need to be prepared
Glue.The formula of OK a karaoke club hydrogel：Carragheen 1.5%, crosslinking agent potassium chloride 1%, water surplus.It weighs 15 gram calories and draws the dispersion of rubber powder end
Into 800 grams of water, in room temperature（About 25 DEG C）Swelling 6 hours.Then, being heated to 95 DEG C makes carragheen thoroughly dissolve.By 10 grams of chlorine
Change potassium to be dissolved in 175 grams of water, be cast into after mixing, after negative pressure degasification with the carrageenan solutions of heating 3-8 millimeters a diameter of
Strip, be placed in 4 DEG C of refrigerators and preserve.Above-mentioned formula is obtained by series of optimum experiment, mainly by adjusting water-setting
The concentration and dosage of crosslinking agent of glue make the 3D printing of preparation have certain mechanical strength, the water for making printing obtain with hydrogel
Gel formpiston has certain intensity, for use in the cast molding of polymeric micro-fluidic chip.The water-setting prepared by this formula
Solution viscosity is low after glue melts, and melts printing convenient for 3D printer.In addition, the hydrogel prints to after melting on cold bottom plate 9
Gelation rate is fast afterwards, is conducive to accumulation molding.
Using computer-aided three-dimensional design software AutoCAD2016 Modeling and Designs and micro-fluidic chip channel network, molten
The corresponding hydrogel male mold of the structural units such as fluid apertures, reactor, the design such as attached drawing of typical list right-angled intersection micro-fluidic chip
1, by split tunnel 2, sample intake passage 7 and solution connection holes（1 and 4-6）It constitutes, microchannel width is about 200 microns, solution
Connect 2 millimeters of bore dia.The height of formpiston is about 150 microns, 65 millimeters of the length of split tunnel 2,12 millimeters of the length of sample intake passage 7, and two
Person connects in the midpoint crossing of sample intake passage 7, and the size of the print size of chip is 75 millimeters × 16 millimeters.Design document exports
The binary STL formatted files that can be directly read for high-accuracy water gel 3D printer are simultaneously stored in SD card, are inserted into water
Start printing in gel 3D printer card reader.
As shown in Fig. 2, it before printing, is dried up after first cleaning glass film plates 9, is placed in the print platform of 3D printer bottom
Upper fixation and after adjusting level, after 3D printing is heated to 80 DEG C of fusings with carragheen thermal reversion hydrogel, injection carries constant temperature
After in the stainless steel syringe of heating device, it is mounted in the screens of hydrogel 3D printer and fixed, startup syringe constant temperature
Heating device.Push syringe piston that the OK a karaoke club hydrogel of thawing is passed through printing by the charging stepper motor of 3D printer
Head squeezes out.Three X-axis of 3D printer, Y-axis and Z axis stepper motors are advanced according to the G code that design document generates, by thawing
OK a karaoke club hydrogel is printed upon on glass film plates 9, is obtained and the structural units such as micro-fluidic chip channel network, solution hole, reactor
Corresponding hydrogel male mold 8.
3D hydrogel printers used in embodiment 1 are commodity high-accuracy water gel printer, and the internal diameter of print head is 100
Micron, can print OK a karaoke club hydrogel formpiston 8 according to STL design documents directly on bottom plate 9.Due to only having microchannel etc.
The position of structural unit prints hydrogel, can substantially save time-write interval and printed material.The more importantly portion of anhydrous gel
Be divided into rigid and smooth glass plate, by casting method can obtain it is smooth carry the isostructural substrate of microchannel, after being conducive to
Continuous encapsulation.When the 3D printer printing hydrogel male mold that the present invention uses, to the heating temperature of OK a karaoke club hydrogel in syringe
Degree control is about 80 DEG C.
Photoinitiator benzoin ethyl ether will be dissolved with（The 0.2% of methyl methacrylate quality）And azodiisobutyronitrile（First
The 0.2% of base methyl acrylate quality）Methyl methacrylate solution heated in 80 DEG C of water-baths 30 minutes can get draw containing light
Send out the methyl methacrylate pre-gathering solutions of agent.Take the 1.5 milliliters of OK a karaoke clubs of mold solution 10 along 3D printing on glass film plates 9
The center line of hydrogel formpiston 8 pours on it, and covers a piece of polymethyl methacrylate cover board 11（75 millimeters × 16 millimeters ×
1.0 millimeter）.It is 0.5 millimeter that the gap of cover board 11 and hydrogel male mold 8 is controlled by gasket, and the gap is required to be full of mold
Solution 10.At room temperature, after twenty minutes can be fully hardened with 365 nanometer ultraviolet ray 12 of wavelength irradiation mold solution 10, poly- methyl
Methyl acrylate cover board 11 then becomes a part for micro-fluidic chip substrate 13.Fig. 3 is using 3D printing OK a karaoke club hydrogel sun
The section microscope photo of polymethyl methacrylate micro flow control chip substrate passageway prepared by mould.It can among 13 surface of substrate
Observe the section of clearly semi-circular channel, about 200 microns of width, depth is about 150 microns, and depth-to-width ratio is higher, to obtaining
The chip package formula of high quality is vital.Finally, in polymethyl methacrylate cover plate 15（75 millimeters × 16 millimeters × 1
Millimeter）Small on piece and 13 microchannel end corresponding position of substrate bore solution connection holes 1,4,5 and 6（See attached drawing 1, aperture 2
Millimeter）, it is aligned and closes with structured one side on substrate 13, applies 2 kg/cms by two smooth glass plywoods
Pressure heats 3 minutes under far-infrared lamp, and taking-up naturally cools to room temperature, that is, completes the encapsulation of substrate 13 and cover plate 15, obtain poly-
Methyl methacrylate micro-fluidic chip finished product 14.
Fig. 4 is to encapsulate to lead to using polymethyl methacrylate micro flow control chip prepared by 3D printing carragheen hydrogel male mold
The section microscope photo in road.Obviously, the unencapsulated channel on micro-fluidic chip substrate 13 obtains good envelope with cover plate 15
Dress, forms semicircular channel, and has the interface between the substrate 13 of channel design and cover plate 15 to disappear, and illustrates that the two has been melted
It is integrated.Fig. 5 is the polymethyl methacrylate micro flow control chip material object photo prepared using 3D printing carragheen formpiston, it is seen that
Chip entire body is transparent, bubble-free, acceptable quality.
The polymethyl methacrylate micro flow control chip that the present invention makes and 0-3000 volts of high-voltage DC power supplies and ampere
Detector constitutes micro-fluidic chip ampere detecting system, and detecting electrode is carbon electrode, and detection current potential is 0.90 volt（Relative to
Silver/silver chloride reference electrode）, it is successfully used for the separation and detection of estriol 16, oestrone 17 and estradiol 18.In 10 mM boron
- 50 mM lauryl sodium sulfate of hydrochlorate（SDS）Mixed solution（pH 9.2）In, grow 65 millimeters micro-fluidic using split tunnel
Chip, separation voltage are+2000 volts.Attached drawing 6 is the electricity containing 0.5 mM estriol, oestrone and estradiol mixed standard solution
Swimming collection of illustrative plates.The detection sensitivity of three kinds of estrogen is respectively 56.68,34.93 and 29.62 nA/mM.The result shows that system of the present invention
Above-mentioned estriol, oestrone and estradiol can be kept completely separate by the polymethyl methacrylate micro flow control chip of work in 200 seconds, high
Effect is quick, has good application prospect in actual sample analysis.
The application of embodiment 2,3D printing agar hydrogel male mold in dimethyl silicone polymer micro flow control chip preparation
The design of micro-fluidic chip and the production method of agar hydrogel male mold are the same as embodiment 1.
77 grams of water are mixed with 2.5 grams of agar powders, standing 3 as a child made agar be swollen.Then, being heated to 90 DEG C makes agar
It is completely dissolved.0.5 gram of borax is dissolved in 20 milliliters of water, two kinds of solution are mixed while hot, room temperature is cooled to and obtains 3D printing water
Gel.
As shown in Fig. 2, it before printing agar hydrogel male mold, is dried up after first cleaning polymethyl methacrylate bottom plate 9,
Apply a small amount of releasing agent（0.5% sodium stearate solution）After dry, be placed on the print platform of 3D printer bottom and fix and adjust
It is horizontal.After 3D printing is heated to 70 DEG C of fusings with agar thermal reversion hydrogel, stainless steel of the injection with constant temperature heating device
It after in syringe, is mounted in the screens of hydrogel 3D printer and fixes, the charging stepper motor for passing through 3D printer pushes
Syringe piston squeezes out the agar hydrogel of thawing by print head.X, Y and three stepper motors of Z axis of 3D printer according to
The G code that design document generates is advanced, and the agar hydrogel layering of thawing is printed upon on polymethyl methacrylate plate 9,
Agar hydrogel male mold corresponding with structural units such as micro-fluidic chip channel network, solution hole, reactors is obtained on bottom plate 9
8。
By 107 room temperature vulcanization dimethyl silicone polymer of commodity dimethyl silicone polymer oligomer and curing agent tetraethoxysilance
It is mixed with accelerating agent dibutyl tin laurate, the dimethyl silicone polymer oligomer mold solution containing curing agent is obtained, wherein just
The content of ethyl silicate and dibutyl tin laurate is respectively 5% and 1.5%；Take 1.5 milliliters of mold solution 10 along bottom plate 9
The center line of 8 long side of 3D printing agar hydrogel male mold pour on it, and cover a piece of transparent dimethyl silicone polymer cover board
11（75 millimeters × 16 millimeters × 1. millimeters）.The gap of cover board 11 and hydrogel male mold 13 is 0.5 millimeter and is full of mold solution
10, cast in the mold solution between hydrogel male mold 8 and cover board 11 with infrared radiation, temperature control is at 45 DEG C, mold solution
Elastomer can be cured as in 20 minutes.After mold solution solidified forming, dimethyl silicone polymer cover board 11 becomes polymerization
A part for object micro-fluidic chip substrate 13 takes micro-fluidic chip made of a piece of reduction with transparent dimethyl silicone polymer thin plate
Cover plate 15（75 millimeters × 16 millimeters × 1.0 millimeters）With washes of absolute alcohol, drying, in position corresponding with 13 upper channel end of substrate
It sets place and beats solution connection holes 1,4,5 and 6（See attached drawing 1, aperture 1-3 millimeters）, substrate 13 and cover plate 15 are 365 nanometers in wavelength
After being irradiated 30 minutes under ultraviolet light, substrate 13 has the one side in channel and is equipped with the dimethyl silicone polymer cover plate 15 of solution connection holes
Alignment, at room temperature pressurization encapsulation can obtain dimethyl silicone polymer micro flow control chip finished product 14.
The application of embodiment 3,3D printing carragheen hydrogel male mold in the preparation of epoxy resin micro-fluidic chip
The design and processing of epoxy resin micro-fluidic chip casting carragheen hydrogel male mold are the same as embodiment 1.By commodity
E51 epoxy resin and curing agent ethylene diamine in mass ratio 90:After 10 mixing and vacuum outgas, it can must contain the epoxy resin of curing agent
Mold solution takes 1.5 milliliters of mold solution 10 to be poured on it along the center line of 8 long side of carragheen hydrogel male mold, and covers one
Piece makes transparent epoxy resin cover board 11 by oneself（75 millimeters × 16 millimeters × 1.0 millimeters）.Cover board 11 and the gap of hydrogel male mold 8 are
0.5 millimeter and be full of mold solution 10.For casting in the epoxy resin between hydrogel male mold 8 and transparent epoxy resin cover board 11
Mold solution is irradiated with infrared ray 12, and temperature control can polymerize hardening, bottom plate 9 is completely at 45 DEG C or so in 25 minutes
Glass plate, ultrasound demould to obtain epoxy resin micro-fluidic chip substrate 13.After mold 10 solidified forming of solution, epoxy resin cover board
11 become a part for polymeric micro-fluidic chip substrate 13.In a piece of self-control epoxy resin cover plate 15（75 millimeters × 16 millimeters
× 1.0 millimeters）Above correspond to and bores solution connection holes 1,4,5 and 6 on substrate 13 at microchannel terminal position（See attached drawing 1, hole
2 millimeters of diameter）, the cover plate 15 after micro-fluidic chip substrate 13 and punching is cleaned and is dried up with water-ethanol, is coated on cover plate 15
Absolute ethyl alcohol one time immediately has substrate 13 one side of channel design to be closed with cover plate 15, is applied by two smooth glass plywoods
Add 3（Kg/cm）Pressure, kept for 10 minutes in 130 DEG C of baking ovens, taking-up naturally cool to room temperature, that is, complete base
The encapsulation of piece 13 and cover plate 15 obtains epoxy resin micro-fluidic chip finished product 14.
Claims (4)
1. a kind of method for preparing polymeric micro-fluidic chip based on hydrogel 3D printing, it is characterised in that the specific steps are：
（1）3D printing agar thermal reversion hydrogel or carragheen thermal reversion hydrogel are prepared, by the concentration for adjusting hydrogel
With use dosage of crosslinking agent, make the 3D printing of preparation that there is certain mechanical strength with hydrogel, after thawing solution viscosity it is low and
Gelation rate is fast after cooling；
（2）Using channel network, solution hole, the structure of reactor unit of computer aided design software design and micro-fluidic chip
Corresponding formpiston generates the design document that 3D printer can be directly read；
（3）After 3D printing carragheen thermal reversion hydrogel or the heating fusing of agar thermal reversion hydrogel, injection adds with constant temperature
In the stainless steel syringe of thermal, syringe is mounted on fixed in the screens of 3D printer；Pass through the charging of 3D printer
Stepper motor pushes syringe piston to squeeze out the hydrogel of fusing by print head；The X-axis of 3D printer, the three of Y-axis and Z axis
Stepper motor is advanced according to the G code generated by design document, and the hydrogel layering of fusing is printed upon glass or polymer
On bottom plate, hydrogel male mold corresponding with micro-fluidic chip channel network, solution hole, structure of reactor unit is obtained；
（4）Macromolecule prepolymer is mixed to obtain to mold solution with curing agent, the mold solution is the methyl-prop containing photoinitiator
E pioic acid methyl ester pre-polymer solution, the dimethyl silicone polymer oligomer containing curing agent or the epoxy resin prepolymer containing curing agent；
Mold solution is poured on 3D printing hydrogel male mold, it is molten full of mold to cover the gap that cover board makes it between hydrogel male mold
Liquid waits for mold solution curing and demolding, obtains the micro-fluidic chip substrate with microchannel structure；By gained substrate and identical material
The micro-fluidic chip cover plate of matter encapsulates to get polymeric micro-fluidic chip finished product；
Step（1）Described in carragheen thermal reversion hydrogel formula：Carragheen 0.5-3%, crosslinking agent potassium chloride 0.1-2%,
Water surplus；The formula of agar hydrogel：Agar 0.5-5%, crosslinking agent borax 0.1-1%, water surplus；
Step（4）In, the group of the methyl methacrylate pre-polymer solution containing photoinitiator is divided into：Methyl methacrylate
Ester, photoinitiator benzoin ethyl ether are the 0.1-0.3% of methyl methacrylate quality, azodiisobutyronitrile, methacrylic acid
The 0.1-0.3% of methyl esters quality；Benzoin ethyl ether, azodiisobutyronitrile are dissolved in methyl methacrylate, at 70-90 DEG C
Water-bath in heat 20-60 minutes, obtain the methyl methacrylate pre-polymer solution containing photoinitiator；It is described containing curing agent
Dimethyl silicone polymer oligomer mold solution be by commodity dimethyl silicone polymer oligomer and curing agent tetraethoxysilance and
The mixing of accelerating agent dibutyl tin laurate obtains, and the content of wherein tetraethoxysilance and dibutyl tin laurate is respectively 5%
And 1-2%；The epoxy resin pattern solution containing curing agent is mixed using commodity bisphenol A epoxide resin with curing agent ethylene diamine
It prepares, wherein the content of ethylenediamine is 8-12%.
2. the method for preparing polymeric micro-fluidic chip according to claim 1 based on hydrogel 3D printing, feature exist
In step（2）Described in design software select and can export the Three-dimensional Design Softwares of binary system STL format design files, including
AutoCAD, 3DMAX, PROE, UG or SOLIDWORKS.
3. the method for preparing polymeric micro-fluidic chip according to claim 1 based on hydrogel 3D printing, feature exist
In step（3）Described in 3D printer be commodity high-accuracy water gel printer, the internal diameter of print head is 50-150 microns, root
Hydrogel male mold is directly printed on bottom plate according to STL design documents, and is only printed at the position for having channel network configuration unit
Hydrogel；When printing hydrogel male mold using 3D printer, to carragheen thermal reversion hydrogel in syringe and agar thermal reversion
The heating temperature of hydrogel is respectively 70-90 DEG C and 60-80 DEG C.
4. the method for preparing polymeric micro-fluidic chip according to claim 1 based on hydrogel 3D printing, feature exist
In step（4）In using 3D printing hydrogel male mold as the polymeric micro-fluidic chip substrate cast molding of template when, macromolecule is pre-
The mold solution that poly solution and curing agent are made into is clipped between 3D printing hydrogel male mold and cover board, between hydrogel male mold and cover board
Gap is 0.25-1.0 millimeters and is full of mold solution, waits for mold solution curing and demolding to get with the micro- of channel network configuration
Fluidic chip substrate.
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| CN107225757A (en) * | 2016-05-16 | 2017-10-03 | 苏州海博智能系统有限公司 | 3D printing fabrication method and system |
| CN106238111A (en) * | 2016-07-28 | 2016-12-21 | 南京理工大学 | A kind of microcapsule preparation method based on micro-fluidic chip shear flow |
| CN106671422B (en) * | 2016-12-20 | 2019-05-17 | 华南理工大学 | A kind of adaptive direct slicing method preparing biological support |
| TWI668064B (en) * | 2017-01-27 | 2019-08-11 | 荷蘭商耐克創新有限合夥公司 | Mold and method of forming the same |
| CN107399075A (en) * | 2017-09-15 | 2017-11-28 | 兰州职业技术学院 | A kind of method that Little Bear bread shaping mould is made using 3D printing technique |
| KR101943968B1 (en) * | 2017-09-25 | 2019-01-30 | (주)아모레퍼시픽 | Apparatus for manufacturing hydrogel pack for skin care and contorl method thereof |
| KR101928401B1 (en) * | 2017-09-25 | 2018-12-12 | (주)아모레퍼시픽 | Apparatus for manufacturing hydrogel pack for skin care and control method thereof |
| CN107813500A (en) * | 2017-10-31 | 2018-03-20 | 上海市格致中学 | A kind of 3D printing platform and operating method |
| CN108007599B (en) * | 2017-11-27 | 2020-11-10 | 中国人民大学 | Biological non-toxic and degradable high-sensitivity temperature sensing chip and preparation method and application thereof |
| CN109880305A (en) * | 2019-01-23 | 2019-06-14 | 西安交通大学 | A kind of method of hydrogel-elastomer composite 3D printing |
| CN110464034B (en) * | 2019-07-25 | 2021-11-16 | 中国农业科学院农产品加工研究所 | Colloid 3D printing system |
| CN110479390A (en) * | 2019-07-31 | 2019-11-22 | 浙江大学 | A kind of sample production method and application based on microwire frame template |
| CN112442215A (en) * | 2019-09-02 | 2021-03-05 | 三纬国际立体列印科技股份有限公司 | Light-cured elastic film capable of adjusting peeling force |
| CN112111073B (en) * | 2020-09-18 | 2023-09-12 | 苏州凝智新材料发展有限公司 | Anti-fatigue full-hydrogel composite material and preparation method and application thereof |
| US20230333096A1 (en) * | 2020-09-24 | 2023-10-19 | University Of Cincinnati | Aptamer sensors with continuous solute passivation |
| CN112892627B (en) * | 2021-02-05 | 2022-04-05 | 浙江大学 | Photocuring micro-fluidic chip based on elastic support body and preparation method and application thereof |
| CN113351268A (en) * | 2021-06-18 | 2021-09-07 | 华南理工大学 | Coaxial micro-fluidic chip based on 3D printing and preparation method thereof |
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